Diethyloctandioldicarbamates and diethyloctandioldiallophanates, method for the production and use thereof

ABSTRACT

Positionally isomeric diethyloctanediol dicarbamates and diethyloctanediol diallophanates, processes for preparing them, and their use as synthesis building blocks and constituents of adhesives, sealing compounds, and coating materials.

This application is a National Phase Application of Patent ApplicationPCT/EP01/00729 filed on 24 Jan. 2001.

The present invention relates to novel positionally isomericdiethyloctanediol dicarbamates and diethyloctanediol diallophanates. Thepresent invention further relates to novel processes for preparing thesenovel compounds. The present invention additionally relates to the useof these novel compounds as synthesis building blocks and asconstituents of adhesives, sealing compounds, and coating materials.Moreover, the present invention relates to novel adhesives, sealingcompounds, and coating materials which comprise the novel compounds. Thepresent invention further relates to novel adhesive films, seals, andcoatings which can be produced with the aid of the novel adhesives,sealing compounds, and coating materials. The present invention relatesnot least to novel primed and unprimed substrates which carry the noveladhesive films, seals, and/or coatings.

The patents U.S. Pat. No. 5,474,811, U.S. Pat. No. 5,356,669, U.S. Pat.No. 5,605,965, WO 94/10211, WO 94/10212, WO 94/10213, EP-A-0 594 068,EP-A-0 594 071 and EP-A-0 594 142 disclose thermally curable coatingmaterials which comprise binders (in this respect, cf. Römpp LexikonLacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998,“Binders”, pages 73 and 74) containing at least one lateral and/orterminal carbamate group of the formula:—O—(CO)—NH₂and at least one crosslinking agent containing at least two functionalgroups which enter into crosslinking reactions with the carbamate group.These known coating compositions provide clearcoats possessing extremelyhigh scratch and etch resistance. Crosslinking agents employed areprimarily highly etherified melamine-formaldehyde resins. Thecrosslinking itself is acid catalyzed, with the catalysts usedpreferably being strong protic acids, especially sulfonic acids, whichin general are blocked with amines.

Moreover, the European patent application 97122649.3-2102 disclosesthermally curable coating materials comprising carbamate-functionalized(cf. the formula above) amino resins. These compounds are used ascrosslinking agents for nonfunctionalized amino resins or for binderscontaining lateral carbamate-reactive functional groups. The coatingmaterials likewise provide coatings having very good performanceproperties.

These known, nitrogen-rich coating materials frequently have a highviscosity, which is detrimental to the application and leveling of thecoating materials. There is therefore a need to lower the viscosity ofthe coating materials without having to reduce their solids content.There is also a need to increase further the proportion of thecomplementary reactive functional groups, especially the proportion ofthe carbamate groups or similar groups, which are needed for thermalcrosslinking. However, this should not involve any further increase inthe hydrophilicity of the coating materials and of the coatings, so asnot to reduce the already high level of acid resistance and moistureresistance.

In this context, the property of being hydrophilic refers to theconstitutional property of a molecule or of a functional group topenetrate the aqueous phase or to remain therein. For further details,reference is made to Römpp, op. cit., “Hydrophilicity”,“Hydrophobicity”, pages 294 and 295.

It is an object of the present invention to provide novelcarbamate-functional and/or allophanate-functional adhesives, sealingcompounds, and coating materials which may be cured thermally, orthermally and with actinic radiation (dual cure), and which no longerhave the disadvantages of the prior art but which instead, with a highsolids content and a high proportion of nitrogen-containing, thermallycrosslinking, complementary reactive functional groups, have acomparatively low viscosity and produce adhesives, sealing compounds,and coatings which have a high acid resistance and moisture resistance.

A further object of the present invention was to provide novel compoundswhich are highly suitable constituents of adhesives, sealing compounds,and coating materials that are curable thermally, or thermally and withactinic radiation.

Yet another object of the present invention was to provide novelcompounds which are able to function as synthesis building blocks inhigh-molecular and low-molecular organic chemistry and in organometallicchemistry.

The invention accordingly provides the novel positionally isomericdiethyloctanediol dicarbamates and diethyloctanediol diallophanates,referred to comprehensively below as the “compounds of the invention”.

The invention also provides novel processes for preparing the compoundsof the invention, which are referred to comprehensively below as the“processes of the invention”.

The invention further provides the novel adhesives, sealing compounds,and coating materials curable thermally, or thermally and with actinicradiation, which comprise the compounds of the invention and/or thecompounds of the invention prepared with the aid of the processes of theinvention and which are referred to below as the “adhesives, sealingcompounds or coating materials of the invention”.

Furthermore, the invention provides the novel adhesive films, seals, andcoatings which can be produced from the adhesives, sealing compounds orcoating materials of the invention and which are referred to below asthe “adhesive films, seals or coatings of the invention”.

Further subject-matter of the invention will emerge from the followingdescription.

In the light of the prior art it was surprising for the skilled workerthat the object on which the present invention is based might beachieved with the aid of the compounds of the invention. A particularsurprise in this context was the ready availability of the compounds ofthe invention and their extremely broad usefulness.

The compounds of the invention contain primary, secondary or tertiarycarbamate groups or allophanate groups. In light of the use in theadhesives, sealing compounds, and coating materials of the invention,the primary and secondary carbamate groups and allophanate groups are ofadvantage and are therefore used with preference. Particular advantages,however, are afforded by primary carbamate groups and allophanategroups, which accordingly are used with particular preference inaccordance with the invention.

The compounds of the invention contain a linear C8 carbon chain.

With regard to the two ethyl groups, the linear C8 carbon chain has thefollowing substitution pattern: 2,3, 2,4, 2,5, 2,6, 2,7, 3,4, 3,5, 3,6or 4,5. In accordance with the invention it is of advantage if the twoethyl groups are in positions 2 and 4, i.e., if the compounds are2,4-diethyloctanediol dicarbamates and 2,4-diethyloctanedioldiallophanates.

With regard to the two hydroxyl groups, the C8 carbon chain has thefollowing substitution pattern: 1,2, 1,3, 1,4, 1,5, 1,6, 1,7, 1,8, 2,3,2,4, 2,5, 2,6, 2,7, 2,8, 3,4, 3,5, 3,6, 3,7, 3,8, 4,5, 4,6, 4,8, 5,6,5,7, 5,8, 6,7, 6,8 or 7,8. In accordance with the invention it is ofadvantage if the two hydroxyl groups are in positions 1 and 5, i.e., ifthe compounds are diethyloctane-1,5-diol dicarbamates ordiethyloctane-1,5-diol diallophanates.

The two substitution patterns are combined with one another in anydesired way; i.e., the compounds of the invention comprise

-   2,3-diethyloctane-1,2-, -1,3-, -1,4-, -1,5-, -1,6-, -1,7-, -1,8-,    -2,3-, -2,4-, -2,5-, -2,6-, -2,7-, -2,8-, -3,4-, -3,5-, -3,6-,    -3,7-, -3,8-, -4,5-, -4,6-, -4,7-, -4,8-, -5,6-, -5,7-, -5,8-,    -6,7-, -6,8- or -7,8-diol,-   2,4-diethyloctane-1,2-, -1,3-, -1,4-, -1,5-, -1,6-, -1,7-, -1,8-,    -2,3-, -2,4-, -2,5-, -2,6-, -2,7-, -2,8-, -3,4-, -3,5-, -3,6-,    -3,7-, -3,8-, -4,5-, -4,6-, -4,7-, -4,8-, -5,6-, -5,7-, -5,8-,    -6,7-, -6,8- or -7,8-diol,-   2,5-diethyloctane-1,2-, -1,3-, -1,4-, -1,5-, -1,6-, -1,7-, -1,8-,    -2,3-, -2,4-, -2,5-, -2,6-, -2,7-, -2,8-, -3,4-, -3,5-, -3,6-,    -3,7-, -3,8-, -4,5-, -4,6-, -4,7-, -4,8-, -5,6-, -5,7-, -5,8-,    -6,7-, -6,8- or -7,8-diol,-   2,6-diethyloctane-1,2-, -1,3-, -1,4-, -1,5-, -1,6-, -1,7-, -1,8-,    -2,3-, -2,4-, -2,5-, -2,6-, -2,7-, -2,8-, -3,4-, -3,5-, -3,6-,    -3,7-, -3,8-, -4,5-, -4,6-, -4,7-, -4,8-, -5,6-, -5,7-, -5,8-,    -6,7-, -6,8- or -7,8-diol,-   2,7-diethyloctane-1,2-, -1,3-, -1,4-, -1,5-, -1,6-, -1,7-, -1,8-,    -2,3-, -2,4-, -2,5-, -2,6-, -2,7-, -2,8-, -3,4-, -3,5-, -3,6-,    -3,7-, -3,8-, -4,5-, -4,6-, -4,7-, -4,8-, -5,6-, -5,7-, -5,8-,    -6,7-, -6,8- or -7,8-diol,-   3,4-diethyloctane-1,2-, -1,3-, -1,4-, -1,5-, -1,6-, -1,7-, -1,8-,    -2,3-, -2,4-, -2,5-, -2,6-, -2,7-, -2,8-, -3,4-, -3,5-, -3,6-,    -3,7-, -3,8-, -4,5-, -4,6-, -4,7-, -4,8-, -5,6-, -5,7-, -5,8-,    -6,7-, -6,8- or -7,8-diol,-   3,5-diethyloctane-1,2-, -1,3-, -1,4-, -1,5-, -1,6-, -1,7-, -1,8-,    -2,3-, -2,4-, -2,5-, -2,6-, -2,7-, -2,8-, -3,4-, -3,5-, -3,6-,    -3,7-, -3,8-, -4,5-, -4,6-, -4,7-, -4,8-, -5,6-, -5,7-, -5,8-,    -6,7-, -6,8- or -7,8-diol,-   3,6-diethyloctane-1,2-, -1,3-, -1,4-, -1,5-, -1,6-, -1,7-, -1,8-,    -2,3-, -2,4-, -2,5-, -2,6-, -2,7-, -2,8-, -3,4-, -3,5-, -3,6-,    -3,7-, -3,8-, -4,5-, -4,6-, -4,7-, -4,8-, -5,6-, -5,7-, -5,8-,    -6,7-, -6,8- or -7,8-diol, or-   4,5-diethyloctane-1,2-, -1,3-, -1,4-, -1,5-, -1,6-, -1,7-, -1,8-,    -2,3-, -2,4-, -2,5-, -2,6-, -2,7-, -2,8-, -3,4-, -3,5-, -3,6-,    -3,7-, -3,8-, -4,5-, -4,6-, -4,7-, -4,8-, -5,6-, -5,7-, -5,8-,    -6,7-, -6,8- or -7,8-diol dicarbamates or diallophanates.

Of these compounds of the invention, 2,4-diethyloctane-1,5-dioldicarbamate and 2,4-diethyloctane-1,5-diol diallophanate, but especially2,4-diethyloctane-1,5-diol dicarbamate, have particular advantages inthe context of their preparation and of their use, and so are used withparticular preference in accordance with the invention.

The preparation of the compounds of the invention starts from thepositionally isomeric diethyloctanediols.

The positionally isomeric diethyloctanediols for use in accordance withthe invention contain a linear C8 carbon chain whose substitutionpattern determines the substitution pattern of the compounds of theinvention.

With regard to the two ethyl groups, the linear C8 carbon chain has thefollowing substitution pattern: 2,3, 2,4, 2,5, 2,6, 2,7, 3,4, 3,5, 3,6or 4,5. In accordance with the invention it is of advantage if the twoethyl groups are in positions 2 and 4, i.e., if the compounds are2,4-diethyloctanediols.

With regard to the two hydroxyl groups, the C8 carbon chain has thefollowing substitution pattern: 1,2, 1,3, 1,4, 1,5, 1,6, 1,7, 1,8, 2,3,2,4, 2,5, 2,6, 2,7, 2,8, 3,4, 3,5, 3,6, 3,7, 3,8, 4,5, 4,6, 4,8, 5,6,5,7, 5,8, 6,7, 6,8 or 7,8. In accordance with the invention it is ofadvantage if the two hydroxyl groups are in positions 1 and 5, i.e., ifthe compounds are diethyloctane-1,5-diols.

The two substitution patterns are combined with one another in anydesired way; i.e., the diethyloctanediols to be used in accordance withthe invention comprise

-   2,3-diethyloctane-1,2-, -1,3-, -1,4-, -1,5-, -1,6-, -1,7-, -1,8-,    -2,3-, -2,4-, -2,5-, -2,6-, -2,7-, -2,8-, -3,4-, -3,5-, -3,6-,    -3,7-, -3,8-, -4,5-, -4,6-, -4,7-, -4,8-, -5,6-, -5,7-, -5,8-,    -6,7-, -6,8- or -7,8-diol,-   2,4-diethyloctane-1,2-, -1,3-, -1,4-, -1,5-, -1,6-, -1,7-, -1,8-,    -2,3-, -2,4-, -2,5-, -2,6-, -2,7-, -2,8-, -3,4-, -3,5-, -3,6-,    -3,7-, -3,8-, -4,5-, -4,6-, -4,7-, -4,8-, -5,6-, -5,7-, -5,8-,    -6,7-, -6,8- or -7,8-diol,-   2,5-diethyloctane-1,2-, -1,3-, -1,4-, -1,5-, -1,6-, -1,7-, -1,8-,    -2,3-, -2,4-, -2,5-, -2,6-, -2,7-, -2,8-, -3,4-, -3,5-, -3,6-,    -3,7-, -3,8-, -4,5-, -4,6-, -4,7-, -4,8-, -5,6-, -5,7-, -5,8-,    -6,7-, -6,8- or -7,8-diol,-   2,6-diethyloctane-1,2-, -1,3-, -1,4-, -1,5-, -1,6-, -1,7-, -1,8-,    -2,3-, -2,4-, -2,5-, -2,6-, -2,7-, -2,8-, -3,4-, -3,5-, -3,6-,    -3,7-, -3,8-, -4,5-, -4,6-, -4,7-, -4,8-, -5,6-, -5,7-, -5,8-,    -6,7-, -6,8- or -7,8-diol,-   2,7-diethyloctane-1,2-, -1,3-, -1,4-, -1,5-, -1,6-, -1,7-, -1,8-,    -2,3-, -2,4-, -2,5-, -2,6-, -2,7-, -2,8-, -3,4-, -3,5-, -3,6-,    -3,7-, -3, 8-, -4,5-, -4,6-, -4,7-, -4,8-, -5,6-, -5,7-, -5,8-,    -6,7-, -6,8- or -7,8-diol,-   3,4-diethyloctane-1,2-, -1,3-, -1,4-, -1,5-, -1,6-, -1,7-, -1,8-,    -2,3-, -2,4-, -2,5-, -2,6-, -2,7-, -2,8-, -3,4-, -3,5-, -3,6-,    -3,7-, -3,8-, -4,5-, -4,6-, -4,7-, -4,8-, -5,6-, -5,7-, -5,8-,    -6,7-, -6,8- or -7,8-diol,-   3,5-diethyloctane-1,2-, -1,3-, -1,4-, -1,5-, -1,6-, -1,7-, -1,8-,    -2,3-, -2,4-, -2,5-, -2,6-, -2,7-, -2,8-, -3,4-, -3,5-, -3,6-,    -3,7-, -3,8-, -4,5-, -4,6-, -4,7-, -4,8-, -5,6-, -5,7-, -5,8-,    -6,7-, -6,8- or -7,8-diol,-   3,6-diethyloctane-1,2-, -1,3-, -1,4-, -1,5-, -1,6-, -1,7-, -1,8-,    -2,3-, -2,4-, -2,5-, -2,6-, -2,7-, -2,8-, -3,4-, -3,5-, -3,6-,    -3,7-, -3,8-, -4,5-, -4,6-, -4,7-, -4,8-, -5,6-, -5,7-, -5,8-,    -6,7-, -6,8- or -7,8-diol, or-   4,5-diethyloctane-1,2-, -1,3-, -1,4-, -1,5-, -1,6-, -1,7-, -1,8-,    -2,3-, -2,4-, -2,5-, -2,6-, -2,7-, -2,8-, -3,4-, -3,5-, -3,6-,    -3,7-, -3,8-, -4,5-, -4,6-, -4,7-, -4,8-, -5,6-, -5,7-, -5,8-,    -6,7-, -6,8- or -7,8-diol.

Particular advantages result from the use of 2,4-diethyloctane-1,5-diol.

The positionally isomeric diethyloctanediols for use in accordance withthe invention are compounds which are known per se and they can beprepared with the aid of customary and known synthesis methods oforganic chemistry such as base-catalyzed aldol condensation or areobtained as by-products of large-scale chemical syntheses such as thepreparation of 2-ethylhexanol.

The compounds of the invention may be prepared in any desired,appropriate way in accordance with the customary and known methods oforganic chemistry, especially of organic nitrogen chemistry. Inaccordance with the invention, however, it is of advantage to preparethem in accordance with the processes of the invention.

The first process of the invention for preparing the positionallyisomeric diethyloctanediol dicarbamates of the invention comprises thereaction of the above-described positionally isomeric diethyloctanediolswith alkyl, cycloalkyl or aryl carbamates, especially methyl, butyl,cyclohexyl or phenyl carbamate, to give the positionally isomericdiethyloctanediol dicarbamates of the invention plus alcohols or phenolsas by-products. The by-products may be separated off in a customary andknown manner, by distillation, for example. Viewed in terms of itsmethod, the process of the invention has no special features but insteadis carried out along the lines of the methods and conditions describedin the patents U.S. Pat. Nos. 4,758,632, 4,301,257 and 2,979,514.

The second process of the invention for preparing the positionallyisomeric diethyloctanediol dicarbamates of the invention comprises thereaction of positionally isomeric diethyloctanediols with phosgene togive the corresponding positionally isomeric chloroformates.

Viewed in terms of its method, the preparation of thechloroformate-functional intermediates has no special features butinstead takes place in accordance with the customary and known methodsof phosgene chemistry, using the corresponding suitable equipment andtaking the safety measures which are customary for the handling ofphosgene.

Advantageously, the reaction with phosgene is conducted at temperaturesof from −10 to 100, preferably from 0 to 50, and in particular from 10to 40° C., depending on the reactivity of the diethyloctanediols and/oron the stirability of the particular solution of the diethyloctanediols.

Although the chloroformate-functional intermediates may be isolated assuch, which may very well be of advantage for specific cases, it isgenerally advisable to react the intermediates in the solution in whichthey are produced with ammonia and/or primary and/or secondary amines.

Examples of suitable primary and secondary amines are those of thegeneral formula INHRR¹  (I),in which the variable R represents a hydrogen atom or representsmonovalent organic radical derived from the following compounds:

-   -   (i) substituted and unsubstituted, linear or branched alkanes,        alkenes, cycloalkanes, cycloalkenes, alkylcycloalkanes,        alkylcycloalkenes, alkenylcycloalkanes or alkenylcycloalkenes        containing no or at least one heteroatom in the chain and/or in        the ring;    -   (ii) substituted and unsubstituted aromatics or heteroaromatics;        and also    -   (iii) alkyl-, alkenyl-, cycloalkyl-, cycloalkenyl-,        alkylcycloalkyl-, alkylcycloalkenyl-, alkenylcycloalkyl- or        alkenylcycloalkenyl-substituted aromatics or heteroaromatics        whose substituents are substituted or unsubstituted and contain        no or at least one heteroatom in their chain and/or their ring;    -   and in which the variable R¹ has the meaning indicated above        with the exception of a hydrogen atom;    -   or in which the radicals R, with the exception of a hydrogen        atom, and R¹ are linked cyclically with one another.

Examples of suitable heteroatoms are oxygen, nitrogen, boron, silicon,sulfur, and phosphorus atoms.

Examples of suitable substituents for the abovementioned radicals R¹ arehalogen atoms, especially fluorine and chlorine atoms, nitro groups, andnitrile groups.

Examples of suitable aromatics are benzene and naphthalene.

Examples of suitable heteroaromatics are thiophene, pyridine, andtriazine.

Examples of suitable alkanes are those having 1 to 20 carbon atoms inthe molecule such as methane, ethane, propane, butane, isobutane,pentane, neopentane, hexane, heptane, octane, isooctane, nonane,dodecane, hexadecane or eicosane.

Examples of suitable alkenes are ethylene and propylene.

Examples of suitable cycloalkanes are cyclopentane and cyclohexane.

Examples of suitable cycloalkenes are cyclopentene and cyclohexene.

Examples of suitable alkylcycloalkanes are methylcyclopentane andmethylcyclohexane.

Examples of suitable alkylcycloalkenes are methylcyclopentene andmethylcyclohexene.

Examples of suitable alkenylcycloalkanes are allyl- andvinylcyclopentane and allyl- and vinylcyclohexane.

Examples of suitable alkenylcycloalkenes are vinylcyclopentene andvinylcyclohexene.

Examples of suitable alkyl, alkenyl, cycloalkyl, cycloalkenyl,alkylcycloalkyl, alkylcycloalkenyl, alkenylcycloalkyl andalkenylcycloalkenyl substituents are methyl, ethyl, propyl, isopropyl,n-butyl, sec-butyl, tert-butyl, vinyl, allyl, cyclohexyl, cyclohexenyl,4-methylcyclohexyl, 4-methylcyclohexenyl, 3-allylcyclohexenyl, and4-vinylcyclohexenyl.

The radicals R¹ are preferably derived from organic compounds which areunsubstituted per se or whose substituents are unsubstituted.

Advantageously, these compounds also contain no heteroatoms in theirchains and/or in their rings and/or in the chains and/or the rings oftheir substituents.

Particular advantages result if the radicals R and R¹ are derived fromlinear alkanes which meet the abovementioned advantageous conditions.Further advantages result if they are derived from methane, ethane,propane, butane, pentane or hexane.

Examples of highly suitable primary amines I are methylamine,ethylamine, propylamine, isobutylamine, hexylamine, cyclohexylamine,allylamine, cyclohexenylamine, aniline, cyclohexylmethylamine,(2-cyclohexyl)ethylamine and benzylamine.

Reaction with these primary amines I results in diethyloctanedioldicarbamates of the invention containing secondary carbamate groups.

Examples of highly suitable secondary amines I are dimethylamine,diethylamine, methylethylamine, dicyclohexylamine,methylcyclohexylamine, dibenzylamine, methylbenzylamine anddiphenylamine.

Examples of highly suitable cyclic amines I are imidazole, thiazine,morpholine, and piperidine.

Reaction with these secondary amines I results in diethyloctanedioldicarbamates of the invention containing tertiary carbamate groups.

Particular advantages result if the radicals R and R¹ are derived fromlinear alkanes which meet the abovementioned advantageous conditions.Further advantages result if they are derived from methane, ethane,propane, butane, pentane or hexane.

Examples of highly suitable primary amines I are methylamine,ethylamine, propylamine, isobutylamine, hexylamine, cyclohexylamine,allylamine, cyclohexenylamine, aniline, cyclohexylmethylamine,(2-cyclohexyl)-ethylamine and benzylamine.

Reaction with these primary amines I results in diethyloctanedioldicarbamates of the invention containing secondary carbamate groups.

Examples of highly suitable secondary amines I are dimethylamine,diethylamine, methylethylamine, dicyclohexylamine, methycyclohexylamine,dibenzylamine, methylbenzylamine and diphenylamine.

Examples of highly suitable cyclic amines I are imidazole, thiazine,morpholine, and piperidine.

Reaction with these secondary amines I results in diethyloctanedioldicarbamates of the invention containing tertiary carbamate groups.

Since diethyloctanediol dicarbamates of the invention which containprimary carbamate groups are very particularly advantageous, ammonia isused with very particular preference in accordance with the invention.

Viewed in terms of method, the reaction of ammonia and/or of amines Iwith the chloroformate-functional intermediates has no special featuresbut instead takes place in accordance with the customary and knownmethods of organic chemistry. The equipment and techniques used for thispurpose are guided in particular by whether solid, liquid or gaseousamines I or gaseous or dissolved ammonia are or is used. The skilledworker will therefore be able to select the appropriate techniques andequipment in a simple manner on the basis of his or her knowledge in theart.

The ammonium chlorides which are produced in the reaction of thechloroformate groups with ammonia or with the amines I are separatedfrom the reaction mixture, comprising the diethyloctanediol dicarbamateof the invention, in a customary and known manner. Examples of suitablemethods are filtration or extraction, it being possible to combine thesemethods with one another in an appropriate way.

The process of the invention for preparing the positionally isomericdiethyloctanediol allophanates of the invention comprises the reactionof the positionally isomeric diethyloctanediols with alkyl, cycloalkylor aryl allophanates, especially alkyl allophanates, particularly methylor ethyl allophanate. In accordance with the invention it is ofadvantage to conduct the reaction at from 50 to 150° C., preferably from60 to 130° C., and in particular from 80 to 120° C. A particularly goodreaction course is ensured if the alcohol and/or phenol are/is removedcontinually from the reaction mixture, by distillation in vacuo, forexample. In order to accelerate the reaction, a customary and knownacidic catalyst such as p-toluene-sulfonic acid may also be added to thereaction mixture.

Depending on the intended use, the compounds of the invention may beisolated following their preparation and prior to their use, or else thesolutions in which they are obtained may be used directly. The preferredvariant is guided in particular by the intended use. For instance, inthe context of their use in solventborne adhesives, sealing compounds,and coating materials, the diethyloctanediol dicarbamates of theinvention will be employed in solution, whereas prior to their use insolvent-free solid or liquid adhesives, sealing compounds and coatingmaterials they are isolated.

Because of their new kinds of structure, the compounds of the inventionmay be used as valuable synthesis building blocks in low-molecular andhigh-molecular organic chemistry and in organometallic chemistry.

The compounds of the invention may further be used for the preparationof adhesives, sealing compounds, and coating materials curable thermallyand/or with actinic radiation. In particular, they are employed asconstituents of the adhesives, sealing compounds, and coating materialsof the invention. In this context, their proportion in the adhesives,sealing compounds, and coating materials of the invention may varyextremely widely. Where the compounds of the invention constitute theprincipal constituent of the adhesives, sealing compounds, and coatingmaterials of the invention, their proportion therein may preferably beup to 95, more preferably 90, with particular preference 85, with veryparticular preference 80, and in particular 75% by weight, based in eachcase on the adhesives, sealing compounds or coating materials of theinvention. Alternatively, the compounds of the invention may be employedas additives in the function of reactive diluents (in this regard, cf.Römpp, op. cit., “Reactive diluents”, p. 491) for the thermalcrosslinking. In this case, just a proportion of preferably from 0.1 to20, more preferably from 0.2 to 18, with particular preference from 0.3to 16, with very particular preference from 0.4 to 14, and in particularfrom 0.5 to 12% by weight, based in each case on the adhesives, sealingcompounds or coating materials of the invention, is sufficient toachieve the advantages of the invention.

The adhesives, sealing compounds or coating materials of the inventionmay further comprise customary and known binders, crosslinking agents,and additives in effective amounts.

The binders may come from any of a very wide variety of oligomer andpolymer classes. Examples of suitable oligomer and polymer classes arerandom, alternating and/or block, linear and/or branched and/or combaddition (co)polymers of ethylenically unsaturated monomers, orpolyaddition resins and/or polycondensation resins. Regarding theseterms, reference is made for further details to Römpp, op. cit., page457, “Polyaddition” and “Polyaddition resins (polyadducts)”, and alsopages 463 and 464, “Polycondensates”, “Polycondensation”, and“Polycondensation resins”. As regards any substituents which may bepresent, the remarks made above apply accordingly.

Examples of highly suitable addition (co)polymers arepoly(meth)acrylates and partially saponified polyvinyl esters.

Examples of highly suitable polyaddition resins and/or polycondensationresins are polyesters, alkyds, polyurethanes, polylactones,polycarbonates, polyethers, epoxy resin-amine adducts, polyureas,polyamides, and polyimides.

Particular advantages result if the above-described binders containcarbamate-reactive functional groups such as N-methylol or N-methylolether groups.

Examples of suitable crosslinking agents are amino resins. Examples ofsuitable amino resins are customary and known, and numerous products areavailable commercially.

Examples of highly suitable amino resins are melamine resins, guanamineresins, and urea resins. In this context it is possible to use any aminoresin suitable for transparent topcoats or clearcoats, or a mixture ofsuch amino resins. For further details, reference is made to Römpp, op.cit., page 29, “Amino resins”, and the textbook “Lackadditive”[Additives for coatings] by Johan Bieleman, Wiley-VCH, Weinheim, N.Y.,1998, pages 242 ff., or to the book “Paints, Coatings and Solvents”,second, completely revised edition, edited by D. Stoye and W. Freitag,Wiley-VCH, Weinheim, N.Y., 1998, pages 80 ff. Also suitable are thecustomary and known amino resins some of whose methylol and/ormethoxymethyl groups have been defunctionalized by means of carbamate orallophanate groups. Crosslinking agents of this kind are described inthe patents U.S. Pat. No. 4,710,542 and EP-B-0 245 700 and also in thearticle by B. Singh and coworkers, “Carbamylmethylated melamines, novelcrosslinkers for the coatings industry” in Advanced Organic CoatingsScience and Technology Series, 1991, volume 13, pages 193 to 207.

Besides these crosslinking agents, further crosslinking agents may alsobe present. Examples of suitable further crosslinking agents are resinsor compounds containing siloxane groups, resins or compounds containinganhydride groups, resins or compounds containing epoxide groups, blockedand/or unblocked polyisocyanates, and/ortris(alkoxycarbonylamino)-triazines, as described in the patents U.S.Pat. No. 4,939,213, U.S. Pat. No. 5,084,541, U.S. Pat. No. 5,288,865 andEP-A-0 604 922.

Depending on the reactivity of the further crosslinking agent, it may beadded directly to the coating materials, adhesives, and sealingcompounds of the invention to give what is known as a one-componentsystem. If, however, it is a particularly reactive crosslinking agent,such as a polyisocyanate or an epoxide, it is generally not added to thecoating materials, adhesives, and sealing compounds of the inventionuntil shortly before use. The result in this case is what is known as atwo-component or multicomponent system.

Where the coating materials, adhesives, and sealing compounds of theinvention are to be curable not only thermally but also with actinicradiation, they include customary and known constituents which can beactivated with actinic radiation. In the context of the presentinvention actinic radiation means electromagnetic radiation, especiallyvisible light, UV light or X-rays, or corpuscular radiation, especiallyelectron beams. The use of UV light is particularly preferred. Examplesof suitable constituents which can be activated with actinic radiationare (meth)acryloyl-, allyl-, vinyl- or dicyclopentadienyl-functional(meth)acrylic copolymers or polyether acrylates, polyester acrylates,unsaturated polyester acrylates, epoxy acrylates, urethane acrylates,amino acrylates, melamine acrylates, silicone acrylates, or thecorresponding methacrylates.

Examples of suitable additives are crosslinking catalysts, initiators,in particular photoinitiators, pigments, dyes, fillers, reinforcingfillers, Theological aids, solvents, wetting agents, dispersants,defoamers, adhesion promoters, additives for improving substratewetting, additives for improving surface smoothness, flatting agents,leveling agents, film-forming auxiliaries, dryers, antiskinning agents,light stabilizers, corrosion inhibitors, biocides, flame retardents,polymerization inhibitors, especially photoinhibitors, or plasticizers,as customary and known, for example, in the plastics or coatings sector.Further examples of suitable additives (C) are described in the textbook“Lackadditive” by Johan Bieleman, Wiley-VCH, Wienheim, N.Y., 1998.

The selection of the additives is guided by the desired profile ofproperties of the coating compositions, adhesives, and sealing compoundsof the invention and by their specific end uses and may therefore bemade by the skilled worker in a simple manner, possibly with theassistance of simple preliminary tests.

The adhesives, sealing compounds, and coating materials of the inventionmay be present in dispersion or solution in aqueous, aqueous-organic ororganic media or may be present as a so-called NAD (non-aqueousdispersion). Furthermore, they may be present in fine division in solidform, as powder coating materials, for example, or in solid formsdispersed in water, as powder slurries, for example. Moreover, they maybe present in solvent-free liquid form, as what are known as 100%systems. The constituents of the adhesives, sealing compounds, andcoating materials of the invention that are required in each case areeasy for the skilled worker to select on the basis of the given profileof properties (solid, liquid, soluble in organic solvents,water-soluble, etc.).

The preparation of the adhesives, sealing compounds, and coatingmaterials of the invention has no special features but instead takesplace in a customary and known manner by mixing of the above-describedconstituents in suitable mixing equipment such as stirred vessels,dissolvers, stirred mills, or extruders in accordance with the methodssuitable for the preparation of the respective adhesives, sealingcompounds, and coating materials of the invention.

The adhesives of the invention are used to produce adhesive films of theinvention on primed and unprimed substrates.

The sealing compounds of the invention are used to produce seals of theinvention on and in primed and unprimed substrates.

The coating materials of the invention may be used as primer-surfacers,solid-color topcoat materials, basecoat materials, and clearcoatmaterials and are used to produce single-coat or multicoat clearcoatsystems or color and/or effect coating sytems on primed and unprimedsubstrates.

Very particular advantages result in the context of their use to produceclearcoat systems, especially in the context of what is known as thewet-on-wet technique, in which a basecoat material, in particular anaqueous basecoat material, is applied to the primed or unprimedsubstrate and dried but not cured, after which a clearcoat material isapplied to the basecoat film and the resultant clearcoat film is curedtogether with the basecoat film, thermally, or thermally and withactinic radiation.

Suitable coating substrates are all surfaces which are not damaged bycuring of the films present thereon using heat or a combination of heatand actinic radiation; examples of such substrates include metals,plastics, wood, ceramic, stone, textile, fiber composites, leather,glass, glass fibers, glass wool, rock wool, mineral-bound andresin-bound building materials, such as plasterboard, cement slabs orroof tiles, and composites of these materials. Accordingly, thecoatings, adhesive films or seals of the invention are also suitable forapplications outside of automotive OEM finishing and automotiverefinish. Here they are particularly suitable for the coating, bondingand/or sealing of furniture and for industrial application, includingcoil coating, container coating, and the impregnation or coating ofelectrical components. In the context of the industrial applications,they are suitable for coating, bonding and/or sealing virtually allparts for private or industrial use, such as radiators, domesticapplicances, small metal parts such as nuts and bolts, hubcaps, wheelrims, packaging, or electrical components such as motor windings ortransformer windings.

In the case of electrically conductive substrates it is possible to useprimers, which are produced in a customary and known manner fromelectrodeposition coating materials. For this purpose both anodic andcathodic electrodeposition coating materials are suitable, butespecially cathodic electrocoats.

It is also possible to coat, bond or seal primed or unprimed plasticsparts made, for example, of ABS, AMMA, ASA, CA, CAB, EP, UF, CF, MF,MPF, PF, PAN, PA, PE, HDPE, LDPE, LLDPE, UHMWPE, PC, PC/PBT, PC/PA, PET,PMMA, PP, PS, SB, PUR, PVC, RF, SAN, PBT, PPE, POM, PUR-RIM, SMC, BMC,PP-EDPM, and UP (abbreviations in accordance with DIN 7728T1).Nonfunctionalized and/or nonpolar substrate surfaces may be subjectedprior to coating in a known manner to a pretreatment, such as with aplasma or by flaming, or may be provided with a water-based primer.

The application of the adhesives, sealing compounds, and coatingmaterials of the invention may take place by any customary applicationmethod, such as spraying, knife coating, brushing, flow coating,dipping, impregnating, trickling or rolling, for example. The substrateto be coated may itself be at rest, with the application equipment beingmoved. Alternatively, the substrate to be coated, especially a coil, maybe moved, with the application unit being at rest relative to thesubstrate or being moved appropriately. Where the adhesives, sealingcompounds, and coating materials of the invention include constituentswhich can be activated with actinic radiation, the application ispreferably carried out in the absence of light.

The applied films of the adhesives, sealing compounds, and coatingmaterials of the invention are cured thermally, or thermally and withactinic radiation, in a customary and known manner, after allowing ifdesired a certain rest period which is used for leveling of the filmsand/or for the evaporation of volatile constituents.

In terms of its method, the thermal curing has no special features butinstead the customary and known temperatures in the range from roomtemperature up to 200° C., curing times in the range from one minute tothree hours, and equipment such as radiant heaters or forced-air ovens,are employed.

Curing with actinic radiation also has no special features in terms ofits method but instead takes place in a customary and known manner byirradiation with UV lamps and/or electron beam sources, preferably underinert gas.

In the context of the curing of the dual-cured adhesives, sealingcompounds, and coating materials of the invention, the thermal curingand curing with actinic radiation may be employed simultaneously oralternately. Where the two curing methods are used alternately, it ispossible, for example, to commence with thermal curing and to end withcuring-with actinic radiation. In other cases it may prove advantageousto commence with curing with actinic radiation and to end with it aswell. The skilled worker is able to determine the curing method mostadvantageous for the case in hand on the basis of his or her generalknowledge in the art, possibly with the assistance of simple preliminarytests.

The adhesive films and seals of the invention produced from theadhesives and sealing compounds of the invention possess outstandingbond strength and sealing capacity, even under extreme climaticconditions and over long periods of time.

The coatings of the invention produced from the coating materials of theinvention exhibit excellent leveling and have an outstanding overallappearance. They are weathering-stable, acid-resistant andmoisture-resistant, and do not yellow even under tropical conditions.They can therefore be used both inside and outside.

Accordingly, the primed and unprimed substrates of the invention,especially bodies of automobiles and commercial vehicles, industrialcomponents, including plastics parts, packaging, coils and electricalcomponents, or furniture, which have been coated with at least onecoating of the invention, sealed with at least one seal of the inventionand/or bonded with at least one adhesive of the invention featureparticular technical and economic advantages, in particular a longservice life, so making them particularly attractive to users.

EXAMPLES Example 1

Preparation of 2,4-diethyloctane-1,5-diol dicarbamate

A 2 l glass apparatus with gas inlet tube, a brine condenser (−15° C.)and a dry-ice condenser was charged with 50 g of toluene and thisinitial charge was saturated with phosgene at from 50 to 55° C. until aphosgene reflux set in. Thereafter, 4 g (2 mol) of2,4-diethyl-1,5-octanediol(hydroxyl number 536 mg KOH/g) in solution in808 g of toluene were reacted with a total of 480 g of phosgene at from50 to 55° C. over the course of 4 hours. Following a post-reactionperiod of 30 minutes at from 50 to 55° C., the reaction mixture wasstripped free of phosgene using nitrogen.

Subsequently, at from room temperature to 40° C., a total of 155 g ofgaseous ammonia was passed in over the course of 2.5 hours, forming awhite precipitate of ammonium chloride. After the end of reaction, at70° C., 400 ml of water were added in order to separate off the ammoniumchloride. The aqueous phase was separated off at 70° C. and the organicphase was washed with twice 400 ml of water at 70° C. Subsequently, theorganic phase was concentrated on a rotary evaporator.

This gave 558 g (96.8%) of 2,4-diethyl-1,5-octanediol dicarbamate havinga hydroxyl number of 27 mg KOH/g. The IR spectrum showed the carbamateband as sole functional group.

Preparation Example 1

The Preparation of a Binder for Use in a Clearcoat Material of theInvention

An appropriate reaction vessel equipped with stirrer, reflux condenserand two feed vessels was charged with 100 parts by weight of a mixtureof 2,4-diethyloctane-1,5-diol, methyl amyl ketone and ethoxyethylpropionate (weight ratio: 1:1:1) and this initial charge was heated to145° C. A mixture of 100 parts by weight of VeoVa® 10 (cf. Römpp, op.cit., “VeoVa®”, page 598), 150 parts by weight of styrene, 100 parts byweight of tert-butylcyclohexyl acrylate, 200 parts by weight of n-butylmethacrylate, 10 parts by weight of 2-hydroxyethyl acrylate and 100parts by weight of isodecyl methacrylate was metered into the initialcharge at a uniform rate over the course of 4.5 hours with stirring. 15minutes before the beginning of this feed stream, the addition of amixture of 40 parts by weight of di-tert-butyl peroxide and methyl amylketone was commenced. This mixture was metered into the resultingreaction mixture at a uniform rate over 5 hours. Followingpostpolymerization, the reaction mixture was adjusted usingmethoxypropyl acetate to a solids content of 74% by weight (one hour at130° C.).

Example 2

Preparation and Application of a Clearcoat Material of the Invention

1 part by weight of 2,4-diethyloctane-1,5-diol dicarbamate (cf. example1), 1 part by weight of a commercial melamine resin (Luwipal® 066 fromBASF Aktiengesellschaft), 121.62 parts by weight of the binder solutionfrom preparation example 1 and 0.28 part by weight of a commercialacidic crosslinking catalyst (Nacure® 4575) were mixed with one another.The resulting clearcoat material was applied to glass in a wet filmthickness of 100 μm and was cured at 130° C. for 30 minutes. Theresulting clearcoat of the invention was clear, transparent,scratch-resistant and acid-resistant.

1. A composition comprising a positionally isomeric diethyloctanedioldicarbamate, a positionally isomeric diethyloctanediol diallophanate, ora positionally isomeric diethyloctanediol dicarbamate and a positionallyisomeric diethyloctanediol diallophanate.
 2. The composition of claim 1,wherein at least one of i) the positionally isomeric diethyloctanedioldicarbamate contains a primary carbamate group, and ii) the positionallyisomeric diethyloctanediol diallophanate contains a primary allophanategroup.
 3. The composition of claim 1, wherein at least one of i) theethyl groups on the linear octane of the positionally isomericdiethyloctanediol dicarbamate have a substitution pattern, with regardto the two ethyl groups, that is one of 2,3; 2,4; 2,5; 2,6; 2,7; 3,4;3,5; 3,6; and 4,5; and ii) the ethyl groups on the linear octane of thepositionally isomeric diethyloctanediol diallophanate have asubstitution pattern, with regard to the two ethyl groups, that is oneof 2,3; 2,4; 2,5; 2,6; 2,7; 3,4; 3,5; 3,6; and 4,5.
 4. The compositionof claim 3, wherein the two ethyl groups are in positions 2 and
 4. 5.The composition of claim 1, wherein at least one of i) the carbamategroups on the linear octane of the positionally isomericdiethyloctanediol dicarbamate have a substitution pattern, with regardto the two carbamate groups, that is one of 1,2; 1,3; 1,4; 1,5; 1,6;1,7; 1,8; 2,3; 2,4; 2,5; 2,6; 2,7; 2,8; 3,4; 3,5; 3,6; 3,7; 3,8; 4,5;4,6; 4,8; 5,6; 5,7; 5,8; 6,7; 6,8; and 7,8, and ii) the allophanategroups of the positionally isomeric diethyloctanediol diallophanate havea substitution pattern, with regard to the two allophanate groups, thatis one of 1,2; 1,3; 1,4; 1,5; 1,6; 1,7; 1,8; 2,3; 2,4; 2,5; 2,6; 2,7;2,8; 3,4; 3,5; 3,6; 3,7; 3,8; 4,5; 4,6; 4,8; 5,6; 5,7; 5,8; 6,7; 6,8;and 7,8.
 6. The composition of claim 5, wherein at least one of i) thetwo carbamate groups are in positions 1 and 5, and ii) the twoallophanate groups are in positions 1 and
 5. 7. The composition of claim6, wherein at least one of i) the positionally isomericdiethyloctanediol dicarbamate is 2,4-diethyloctane-1,5-diol dicarbamate,and ii) the positionally isomeric diethyloctanediol diallophanate is2,4-diethyloctane-1,5-diol diallophanate.
 8. The composition of claim 1,wherein at least one of i) the hydroxyl groups on the linear octane ofthe positionally isomoric diethyloctanediol dicarbamate have asubstitution pattern, with regard to the two hydroxyl groups, that isone of 1,2; 1,3; 1,4; 1,5; 1,6; 1,7; 1,8; 2,3; 2,4; 2,5; 2,6; 2,7; 2,8;3,4; 3,5; 3,6, 3,7; 3,8; 4,5; 4,6; 4,8; 5,6; 5,7; 5,8; 6,7; 6,8; and7,8, and ii) the hydroxyl groups on the linear octane of thepositionally isomeric diethyloctanediol diallophanate have asubstitution pattern, with regard to the two hydroxyl groups, that isone of 1,2; 1,3; 14; 1,5; 1,6; 1,7; 1,8; 2,3; 2,4; 2,5; 2,6; 2,7; 2,8;3,4; 3,5; 3,6; 3,7; 3,8; 4,5; 4,6; 4,8; 5,6; 5,7; 5,8; 6,7; 6,8; and7,8.
 9. The composition of claim 8, wherein the two hydroxyl groups arein positions 1 and
 5. 10. A method comprising reacting the positionallyisomeric diethyloctanediol dicarbamate, the positionally isomericdiethyloctanediol diallophanate, or the positionally isomericdiethyloctanediol dicarbamate and the positionally isomericdiethyloctanediol diallophanate of claim 1 to form a reaction product.11. The reaction product produced by the method of claim 10, wherein thereaction product is one of an adhesive, a sealing compound, a coatingmaterial, wherein the coating material is curable by one of i) thermallyand ii) thermally and with actinic radiation.
 12. A composition formedfrom the reaction product of claim 11, wherein the composition is one ofan adhesive film, a seal, and a coating.
 13. A substrate comprising thecomposition of claim 12, wherein the substrate is one of primed andunprimed.